JPWO2005064367A1 - Polarizing plate protective film, polarizing plate with antireflection function and optical product - Google Patents

Abstract

In the present invention, a base film and a formula (1): MXn (M represents a metal atom or a semimetal atom, X represents an alkoxyl group, etc., and n represents a valence of M on the base film. ), Or a part of the compound represented by the formula (1) or a completely hydrolyzed product, in the molecule,-(OM) m-O- (wherein M represents the same meaning as described above, and m represents a natural number.) A low refractive index containing a metal oxide composite having a bond and inorganic fine particles and having a refractive index of 1.25 to 1.37. A polarizing plate protective film having a layer, a polarizing plate with an antireflection function using the polarizing plate protective film, and an optical product including the polarizing plate with an antireflection function. According to the present invention, it has a low refractive index layer having an antireflection effect, has sufficient scratch resistance as a protective film for a polarizing plate, and has little warping of the film when bonded to the polarizing plate. A polarizing plate protective film, a polarizing plate with an antireflection function, and an optical product are provided.

Description

  The present invention relates to a polarizing plate protective film, a polarizing plate with an antireflection function, and an optical product including the polarizing plate with an antireflection function.

  In recent years, in a display such as a liquid crystal display, a method of forming a low refractive index layer using a low refractive index material on a transparent substrate (base film) is known in order to prevent a decrease in visibility due to surface reflection. .

As conventional low refractive index materials, inorganic materials such as MgF ₂ and SiO ₂ ; organic materials such as perfluororesin; and the like are known. In order to obtain high antireflection performance, it is preferable that the difference between the refractive index of the layer having a high refractive index (high refractive index layer) and the low refractive index layer is larger because the minimum value of the reflectance is smaller. . However, since the difference in refractive index between the base film and the low refractive index material is small, it is necessary to form a multilayer film in which a layer made of a higher refractive index material and a low refractive index layer are laminated on the base film surface. was there.

  In recent years, several methods for forming a low refractive index layer using hollow silica-based fine particles having a low refractive index have been proposed. For example, Japanese Patent Application Laid-Open No. 2001-233611 discloses a method of forming a transparent film having a low refractive index by applying and drying a coating material composition obtained by dispersing hollow silica-based fine particles in a matrix-forming material. It is disclosed. JP-A-2003-201443 discloses a porous matrix having a low refractive index by applying and drying a coating material composition obtained by dispersing hollow silica-based fine particles in a matrix-forming material. A method for forming the formed transparent coating is disclosed. According to these methods, high antireflection performance can be obtained without laminating a high refractive index layer and a low refractive index layer.

  However, although the method described in the above document forms a matrix containing hollow silica-based fine particles, the polarizing plate of a liquid crystal display device or the like is used because the strength of the obtained matrix is weak and the cohesive force is poor. In some cases, the scratch resistance required as a protective film is insufficient, which is a problem. Moreover, when it is bonded to a polarizing plate and incorporated in a liquid crystal display device, high dimensional stability is required, but warpage (deformation) may occur.

  The present invention has been made in view of the above-described prior art, has a low refractive index layer effective as an antireflection layer, has sufficient scratch resistance as a protective film for a polarizing plate, and It is an object of the present invention to provide a polarizing plate protective film with less warping (deformation) of a film that causes a problem when bonded to a polarizing plate, and a polarizing plate with an antireflection function. Moreover, this invention makes it a subject to provide the optical product using the polarizing plate with an antireflection function of this invention.

  As a result of intensive research aimed at solving the above-mentioned problems, the present inventors have found that a specific metal compound or a metal oxide composite formed from all or a partial hydrolysis product of the metal compound on a transparent substrate film It has been found that a polarizing plate protective film having a body and inorganic fine particles and having a low refractive index layer in which the refractive index is adjusted within a certain range has an excellent antireflection function and scratch resistance. Moreover, when using what consists of alicyclic structure containing polymer resin as a base film, the polarizing plate protective film with few curvature (deformation) of the film which becomes a problem at the time of bonding with a polarizing plate. As a result, the present invention was completed.

Thus, according to the first aspect of the present invention, the following polarizing plate protective films (1) to (8) are provided.
(1) A polarizing plate protective film having a base film and a low refractive index layer formed on the base film,
The low refractive index layer has the formula (1): MX _n (wherein M represents a metal atom or a metalloid atom, X represents a halogen atom, a monovalent hydrocarbon group which may have a substituent, An oxygen atom, an organic acid group, a β-diketonate group, an inorganic acid group, an alkoxyl group or a hydroxyl group, and n represents a valence of M. When n is 2 or more, X may be the same or different. A group consisting of at least one partial hydrolysis product of the compound represented by the formula (1) and at least one complete hydrolysis product of the compound represented by the formula (1) A metal oxide having a bond of-(OM) _m -O- (wherein M represents the same meaning as described above and m represents a natural number) formed in one or more types selected from Containing a composite material and inorganic fine particles and having a refractive index of 1.25 to 1.37 Polarizing plate protective film characterized in that there.
(2) The polarizing plate protective film according to (1), wherein the inorganic fine particles are hollow fine particles of an inorganic compound.

(3) The polarizing plate protective film according to (1) or (2), wherein M is Si.
(4) The polarizing plate protective film according to any one of (1) to (3), wherein a hard coat layer is interposed between the base film and the low refractive index layer.

(5) The polarizing plate protective film according to (4), wherein the hard coat layer contains an active energy ray-curable resin or a thermosetting resin.
(6) The polarizing plate protective film according to (4), wherein the refractive index of the hard coat layer is 1.53 or more.
(7) The polarizing plate protective film according to (4), wherein the hard coat layer further contains conductive fine particles.
(8) The polarizing plate protective film according to any one of (1) to (7), wherein the base film is made of an alicyclic structure-containing polymer resin.

According to the second aspect of the present invention, there is provided the following polarizing plate with antireflection function (9).
(9) A polarizing plate with an antireflection function, wherein the polarizing plate protective film of the present invention is used on the viewing side of the protective film of the polarizing plate.
According to the third aspect of the present invention, the following optical product (10) is provided.
(10) An optical product comprising the polarizing plate with an antireflection function of the present invention.

It is a figure which shows the method of measuring the curvature rate of the synthetic resin which comprises a base film. It is layer structure sectional drawing of the polarizing plate protective film of this invention. It is layer structure sectional drawing of the polarizing plate with an antireflection function of this invention. It is layer structure sectional drawing which bonded the polarizing plate with an antireflection function of this invention to the liquid crystal display cell. FIG. 5 is a cross-sectional view of the layer structure of the liquid crystal display cell shown in FIG. 4.

  Hereinafter, the present invention will be described in detail by dividing it into 1) a polarizing plate protective film, 2) a polarizing plate with an antireflection function, and 3) an optical product.

1) Polarizing plate protective film The polarizing plate protective film of the present invention has a base film and a low refractive index layer formed on the base film.

(Base film)
Although the base film used for this invention will not be restrict | limited especially if it consists of a synthetic resin excellent in transparency, what consists of a synthetic resin whose thickness of 1 mm and a total light transmittance is 80% or more is preferable. Examples of the synthetic resin constituting the base film include an alicyclic structure-containing polymer resin, polycarbonate resin, polyester resin, polysulfone resin, polyethersulfone resin, polystyrene resin, chain polyolefin resin, polyvinyl alcohol resin, and cellulose acetate. Resins, polyvinyl chloride resins, polymethacrylate resins and the like can be mentioned.

  Among these, from the viewpoint of low birefringence, an alicyclic structure-containing polymer resin or a cellulose acetate resin such as triacetyl cellulose is preferable, from the viewpoint of transparency, low hygroscopicity, dimensional stability, light weight, etc. The use of one or more of the alicyclic structure-containing polymer resins is particularly preferred.

  The alicyclic structure-containing polymer resin has an alicyclic structure in the repeating unit of the polymer resin, and the polymer resin having an alicyclic structure in the main chain and an alicyclic structure in the side chain. Any polymer resin can be used.

  Examples of the alicyclic structure include a cycloalkane structure and a cycloalkene structure, and a cycloalkane structure is preferable from the viewpoint of thermal stability. Although there is no restriction | limiting in particular in carbon number which comprises an alicyclic structure, Usually, 4-30 pieces, Preferably it is 5-20 pieces, More preferably, it is 5-15 pieces. When the number of carbon atoms constituting the alicyclic structure is in this range, a base film excellent in heat resistance and flexibility can be obtained.

  The proportion of the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer resin may be appropriately selected according to the purpose of use, but is usually 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more. If the number of repeating units having an alicyclic structure is too small, the heat resistance is undesirably lowered. In addition, repeating units other than the repeating unit which has an alicyclic structure in an alicyclic structure containing polymer resin are suitably selected according to the intended purpose.

  Specific examples of the alicyclic structure-containing polymer resin include (i) a norbornene polymer, (ii) a monocyclic olefin polymer, (iii) a cyclic conjugated diene polymer, and (iv) a vinyl alicyclic ring. Formula hydrocarbon polymers, hydrides thereof and the like. Among these, norbornene-based polymers are preferable from the viewpoints of transparency and moldability.

  Specific examples of the norbornene-based polymer include ring-opening polymers of norbornene-based monomers, ring-opening copolymers of norbornene-based monomers and other monomers capable of ring-opening copolymerization, and those Hydrides of the above, addition polymers of norbornene monomers, addition copolymers with other monomers copolymerizable with norbornene monomers, and the like. Among these, from the viewpoint of transparency, a ring-opening (co) polymer hydride of a norbornene monomer is particularly preferable.

Examples of the norbornene-based monomer include bicyclo [2.2.1] hept-2-ene (common name: norbornene), tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene. (Common name: dicyclopentadiene), 7,8-benzotricyclo [4.3.0.1 ^2,5 ] dec-3-ene (common name: methanotetrahydrofluorene), tetracyclo [4.4.0. 1 ^2,5 . 1 ^7,10 ] dodec-3-ene (common name: tetracyclododecene), derivatives of these compounds (for example, those having a substituent in the ring), and the like. Here, examples of the substituent include an alkyl group, an alkylene group, an alkoxycarbonyl group, and a carboxyl group. In addition, these substituents may be the same or different and a plurality may be bonded to the ring. Norbornene monomers can be used alone or in combination of two or more.

  Other monomers capable of ring-opening copolymerization with norbornene monomers include, for example, monocyclic olefins such as cyclohexene, cycloheptene, and cyclooctene and derivatives thereof; cyclic conjugated dienes such as cyclohexadiene and cycloheptadiene; Derivatives thereof; and the like.

Ring-opening polymers of norbornene monomers and ring-opening copolymers of norbornene monomers and other monomers copolymerizable therewith are polymerized in the presence of a ring-opening polymerization catalyst. Can be obtained.
As the ring-opening polymerization catalyst, a commonly used known catalyst can be used.

  Examples of other monomers that can be addition-copolymerized with norbornene-based monomers include, for example, α-olefins having 2 to 20 carbon atoms such as ethylene and propylene, and derivatives thereof; cycloolefins such as cyclobutene and cyclopentene, and these Derivatives; non-conjugated dienes such as 1,4-hexadiene and the like. These monomers can be used alone or in combination of two or more. In these, an alpha olefin is preferable and ethylene is more preferable.

  Norbornene monomer addition polymers and addition copolymers of norbornene monomers and other monomers copolymerizable therewith are obtained by polymerizing the monomers in the presence of an addition polymerization catalyst. Obtainable. As the addition polymerization catalyst, a commonly used known catalyst can be used.

  Ring-opening polymer of norbornene monomer, ring-opening copolymer of norbornene monomer and other monomer capable of ring-opening copolymerization, addition polymer of norbornene monomer, and norbornene Addition of a known hydrogenation catalyst to the hydride of an addition polymer of a system monomer and another monomer copolymerizable therewith, preferably hydrogenates a carbon-carbon unsaturated bond by 90% or more. Can be obtained.

Examples of the monocyclic olefin-based polymer include addition polymers such as cyclohexene, cycloheptene, and cyclooctene.
Examples of the cyclic conjugated diene polymer include polymers obtained by 1,2-addition polymerization or 1,4-addition polymerization of cyclic conjugated diene monomers such as cyclopentadiene and cyclohexadiene.

  The vinyl alicyclic hydrocarbon polymer is a polymer having a repeating unit derived from vinylcycloalkane or vinylcycloalkene. Examples of the vinyl alicyclic hydrocarbon polymer include polymers of vinyl alicyclic hydrocarbon compounds such as vinyl cycloalkanes such as vinyl cyclohexane, vinyl cycloalkenes such as vinyl cyclohexene, and hydrides thereof; styrene, α-methyl Examples thereof include hydrides of aromatic ring portions of polymers of vinyl aromatic hydrocarbon compounds such as styrene.

  The vinyl alicyclic hydrocarbon polymer is a random copolymer of a vinyl alicyclic hydrocarbon compound or a vinyl aromatic hydrocarbon compound and another monomer copolymerizable with these monomers, It may be a hydride of a copolymer such as a block copolymer. Examples of the block copolymerization include diblock, triblock, or more multiblock and gradient block copolymerization, but are not particularly limited.

  The molecular weight of the synthetic resin is usually from 10,000 to 300 in terms of weight average molecular weight in terms of polyisoprene or polystyrene measured by gel permeation chromatography using cyclohexane (toluene if the polymer resin does not dissolve) as a solvent. 5,000, preferably 15,000-250,000, more preferably 20,000-200,000, the mechanical strength and moldability of the base film are highly balanced and suitable. .

  The glass transition temperature of the synthetic resin may be appropriately selected according to the purpose of use, but is preferably 80 ° C. or higher, more preferably 100 to 250 ° C. A base film made of a synthetic resin having a glass transition temperature in such a range is excellent in durability without being deformed or stressed when used under high temperature and high humidity.

  The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the synthetic resin is not particularly limited, but is usually in the range of 1 to 10, preferably 1 to 6, and more preferably 1.1 to 4. . By adjusting the molecular weight distribution in such a range, the mechanical strength and molding processability of the base film are well balanced.

The base film used in the present invention can be obtained by molding the above synthetic resin into a film by a known molding method.
Examples of the method for molding the synthetic resin into a film include a solution casting method and a melt extrusion molding method. Among these, the melt extrusion molding method is preferable because the content of volatile components in the film and the thickness unevenness can be reduced. Further, examples of the melt extrusion method include a method using a die such as a T die, an inflation method, and the like, but a method using a T die is preferable in terms of excellent productivity and thickness accuracy.

  When adopting a method using a T die as a method for forming a film, the melting temperature of the synthetic resin in the extruder having the T die is preferably 80 to 180 ° C. higher than the glass transition temperature of the synthetic resin. More preferably, the temperature is higher by 100 to 150 ° C. If the melting temperature in the extruder is excessively low, the fluidity of the synthetic resin may be insufficient. Conversely, if the melting temperature is excessively high, the resin may be deteriorated. Furthermore, it is preferable to pre-dry the synthetic resin to be used before forming into a film. The preliminary drying is performed using, for example, a hot air dryer or the like in the form of pellets or the like. The drying temperature is preferably 100 ° C. or more, and the drying time is preferably 2 hours or more. By performing preliminary drying, the amount of volatile components in the film can be reduced, and foaming of the extruded synthetic resin can be prevented.

  The substrate film preferably has a saturated water absorption of 0.05% by weight or less, more preferably 0.01% by weight or less, and particularly preferably 0.007% by weight or less. By using a material having a saturated water absorption rate within the above range, the adhesiveness with the low refractive index layer is increased, and the low refractive index layer is not peeled even after long-term use.

  Moreover, as a base film, what gave the surface modification process to the single side | surface or both surfaces can be used. By performing the surface modification treatment, adhesion to the low refractive index layer and other layers described later can be improved. Examples of the surface modification treatment include energy beam irradiation treatment and chemical treatment.

  Examples of the energy ray irradiation treatment include corona discharge treatment, plasma treatment, electron beam irradiation treatment, ultraviolet ray irradiation treatment, and the like. From the viewpoint of treatment efficiency, corona discharge treatment and plasma treatment are preferred, and corona discharge treatment is particularly preferred. The chemical treatment may be performed by immersing in an aqueous oxidizing agent solution such as potassium dichromate solution or concentrated sulfuric acid and then thoroughly washing with water. It is effective to shake in the immersed state, but there is a problem that the surface dissolves or transparency decreases when treated for a long period of time, depending on the reactivity, concentration, etc. of the chemical used, the treatment time etc. It needs to be adjusted.

  Although the thickness of a base film is 10-1000 micrometers normally, from a viewpoint of transparency and mechanical strength, Preferably it is 30-300 micrometers, More preferably, it is 40-200 micrometers.

  In the polarizing plate protective film of the present invention, other layers can be interposed between the base film and the low refractive index layer. Examples of other layers include a hard coat layer and a primer layer, but it is preferable to interpose a hard coat layer. By interposing the hard coat layer, it is possible to obtain a polarizing plate protective film having more excellent surface hardness.

  The hard coat layer is formed for the purpose of reinforcing the surface hardness, repeated fatigue resistance and scratch resistance of the base film. The material for forming the hard coat layer is not particularly limited as long as it shows a hardness of “HB” or higher in the pencil hardness test specified in JIS K5600-5-4, but productivity, adhesiveness, transparency and From the viewpoint of excellent mechanical strength, it is preferable to contain a thermosetting resin or an active energy ray curable resin, and more preferably an active energy ray curable resin.

Examples of the thermosetting resin include phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea cocondensation resin, silicone resin, poly Examples thereof include siloxane resins. Among these, melamine resins, epoxy resins, silicone resins, and polysiloxane resins are preferable from the viewpoint of excellent surface hardness, resistance to repeated fatigue, and scratch resistance.
Further, these resins can be used by adding a curing agent such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier and the like, if necessary.

  The active energy ray-curable resin is a resin obtained by curing a prepolymer, an oligomer and / or a monomer having a polymerizable unsaturated bond or an epoxy group in a molecule by irradiation with energy rays. An active energy ray refers to an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or crosslinking molecules, and usually an ultraviolet ray or an electron beam is used.

  Examples of prepolymers and oligomers having a polymerizable unsaturated bond or epoxy group in the molecule include unsaturated polyesters such as a condensation product of unsaturated dicarboxylic acid and polyhydric alcohol; polyester methacrylate, polyether methacrylate, polyol methacrylate And methacrylates such as melamine methacrylate, polyester acrylates, epoxy acrylates, urethane acrylates, polyether acrylates, polyol acrylates, acrylates such as melamine acrylates, and cationic polymerization type epoxy compounds.

  Examples of the monomer having a polymerizable unsaturated bond or an epoxy group in the molecule include styrene monomers such as styrene and α-methylstyrene; methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, methoxy acrylate Acrylic acid esters such as ethyl; methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate; acrylic acid-2- (N, N-diethylamino) ethyl, acrylic acid-2- (N, N- Unsaturated substituted amino alcohol esters such as dimethylamino) ethyl and acrylic acid-2- (N, N-dibenzylamino) methyl; unsaturated carboxylic acid amides such as acrylamide and methacrylamide; ethylene glycol diacrylate, Propylene glycol diacrylate, neo Multifunctional acrylates such as n-glycol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, etc .; trimethylolpropane trithio And polythiols having two or more thiol groups in the molecule, such as glycolate, trimethylolpropane trithiopropylate, and pentaerythritol tetrathioglycolate. In the present invention, prepolymers, oligomers and / or monomers having a polymerizable unsaturated bond or an epoxy group in these molecules can be used singly or in combination of two or more.

  In the polarizing plate protective film of the present invention, the hard coat layer preferably contains conductive fine particles in addition to the active energy ray-curable resin or thermosetting resin. By containing conductive fine particles in the active energy ray-curable resin or thermosetting resin, it has a function as an antistatic film, and at the same time, it has excellent mechanical strength and can form a high refractive index hard coat layer. it can.

  The conductive fine particles are not particularly limited as long as they are conductive fine particles, but metal oxide fine particles are preferable because of excellent transparency.

  Examples of the conductive metal oxide include antimony pentoxide, tin oxide (PTO) doped with phosphorus, tin oxide, tin oxide doped with antimony (ATO), and tin oxide doped with fluorine (FTO). Indium oxide doped with tin (ITO), indium oxide doped with zinc (IZO), zinc oxide doped with aluminum (AZO), zinc oxide / aluminum oxide, zinc antimonate and the like. These metal oxides can be used alone or in combination of two or more. Among these, the use of tin oxide doped with antimony pentoxide and / or phosphorus is preferable because of its excellent transparency.

  Moreover, in this invention, what provided electroconductivity by coat | covering a conductive metal oxide to the metal oxide fine particle which does not have electroconductivity as a conductive metal oxide fine particle can also be used. For example, the surface of fine particles of titanium oxide, zirconium oxide, cerium oxide or the like having a high refractive index but no conductivity can be used by coating the conductive metal oxide to impart conductivity.

  The BET average particle diameter of the metal oxide fine particles is usually 200 nm or less, preferably 50 nm or less, so as not to lower the transparency of the hard coat layer. When it is larger than 200 nm, haze (turbidity) increases. The particle diameter should be measured by visual observation of secondary electron emission image photographs obtained by a scanning electron microscope (SEM) or by a particle size distribution meter using a dynamic light scattering method, a static light scattering method, or the like. Can do.

The hard cord layer is obtained by applying a coating liquid for constituting the hard coat layer, curing and drying.
The coating liquid for constituting the hard coat layer is a thermosetting resin or a prepolymer, oligomer and / or having a polymerizable unsaturated bond or epoxy group in the molecule for constituting the active energy ray curable resin. It can be prepared by dissolving or dispersing the monomer, conductive fine particles and additives in a suitable organic solvent.

  Examples of the organic solvent used include alcohols such as methanol, ethanol, isopropanol and n-butanol; glycols such as ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol, diethylene glycol monobutyl ether and diacetone glycol Aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as n-hexane and n-heptane; esters such as ethyl acetate and butyl acetate; ketones such as methyl ethyl ketone and methyl isobutyl ketone; methyl ethyl ketoxime and the like Examples include oximes; cell solves such as ethyl cell solve and butyl cell solve; and combinations of two or more thereof.

  The content of the prepolymer, oligomer and / or monomer in the coating liquid is not particularly limited, but since excellent coating suitability is obtained, the prepolymer, oligomer and / or monomer is 5% by weight to 95% by weight. % Content is preferred.

  In the case where conductive fine particles are contained in the hard coat layer, the content of the conductive fine particles in the coating liquid is not particularly limited, but is preferably 30% by volume or more, more preferably 40% in the coating liquid. % To 70% by volume. When the blending amount of the conductive fine particles is less than 30% by volume, the antistatic property of the obtained polarizing plate protective film becomes poor.

  Moreover, when hardening of a hard-coat layer is performed by ultraviolet irradiation, a photoinitiator and a photoinitiator are added to a coating liquid. As photopolymerization initiators, radical polymerization initiators such as acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether; aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, metallocene compounds, benzoin sulfonic acids Cationic polymerizable initiators such as esters; These can be used individually by 1 type or in combination of 2 or more types. The addition amount of the photopolymerization initiator is usually 0.1 to 100 parts by weight of the prepolymer, oligomer and / or monomer having a polymerizable unsaturated bond or epoxy group in the molecule for forming the hard coat layer. 10 parts by weight. Further, n-butylamine, triethylamine, tri-n-butylphosphine and the like can be mixed and used as a photosensitizer in the coating solution.

An organic reactive silicon compound can be further added to the coating solution. Examples of the organic reactive silicon compound used include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, Such as methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethylethoxysilane, dimethylmethoxysilane, dimethylpropoxysilane, dimethylbutoxysilane, methyldimethoxysilane, methyldiethoxysilane , Formula: R _m Si (OR ′) _n (wherein, R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ′ represents an alkyl group having 1 to 10 carbon atoms. Independently, m . N = a positive integer satisfying 4 relationship) organic silicon compounds represented by;

  γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-aminopropyltriethoxysilane , Γ-methacryloxypropylmethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilazane, vinyltris (β-methoxy Silane coupling agents such as ethoxy) silane;

  One-end vinyl group-substituted polysilane, both-end vinyl group-substituted polysilane, one-end vinyl group-substituted polysiloxane, both-end vinyl group-substituted polysiloxane, vinyl group-substituted polysilane obtained by reacting these compounds, or vinyl group-substituted poly Active energy ray-curable silicon compounds such as siloxane; other organosilicon compounds such as (meth) acryloxysilane compounds such as 3- (meth) acryloxypropyltrimethoxysilane and 3- (meth) acryloxypropylmethyldimethoxysilane And the like.

  A leveling agent and a dispersant can be appropriately added to the coating solution for the purpose of improving the uniformity and adhesion of the coating film. Examples of the leveling agent to be used include compounds that lower the surface tension such as silicone oil, fluorinated polyolefin, and polyacrylic ester, and examples of the dispersing agent include surfactants and silane coupling agents.

  For the purpose of imparting antiglare properties, particles that impart antiglare properties may be added to the coating solution. The particles imparting antiglare properties are not particularly limited as long as irregularities are formed on the surface of the antiglare layer. In order to effectively form irregularities on the surface of the antiglare layer, the average particle size is preferably 0.5 to 10 μm, and more preferably 1 to 7 μm.

The method for forming the hard coat layer is not particularly limited. For example, a coating liquid for forming the hard coat layer is applied onto the substrate film by a known coating method, dried, heated, or activated energy rays. And a method of curing by irradiation.
The heating temperature and heating time, the irradiation intensity of the active energy ray, the irradiation time, and the like are not particularly limited, and the curing conditions may be appropriately set according to the type of material constituting the hard coat layer.
The thickness of the hard coat layer is usually 0.5 to 30 μm, preferably 1 to 10 μm. If the thickness of the hard coat layer is less than 0.5 μm, the hardness and mechanical strength of the layer will be poor. On the other hand, if it is more than 30 μm, unevenness in thickness tends to occur when applied, and workability may be deteriorated.

The refractive index of the hard coat layer is preferably 1.53 or more, more preferably 1.55 or more. When the refractive index of the hard coat layer is within this range, reflection of external light can be suppressed and reflection can be prevented. The refractive index can be obtained by measuring using, for example, a known spectroscopic ellipsometer.
The hard coat layer preferably has an antistatic function. Specifically, the surface resistance value of the hard coat layer is preferably 1.0 × 10 ¹⁰ Ω / □ or less, more preferably 5.0 × 10 ⁹ Ω / □ or less.
The surface resistance value can be measured using a resistivity meter.

  The primer layer is formed for the purpose of imparting and improving adhesion between the base film and the hard coat layer or the low refractive index layer. Examples of the material constituting the primer layer include polyester urethane resin, polyether urethane resin, polyisocyanate resin, polyolefin resin, resin having a hydrocarbon skeleton in the main chain, polyamide resin, acrylic resin, polyester resin, vinyl chloride / acetic acid Examples thereof include vinyl copolymers, chlorinated rubbers, cyclized rubbers, and modified products obtained by introducing polar groups into these polymers. Among these, a modified product of a resin having a hydrocarbon skeleton in the main chain and a modified product of a cyclized rubber can be suitably used.

  Examples of the resin having a hydrocarbon skeleton in the main chain include a polybutadiene skeleton or a resin having a polybutadiene skeleton hydrogenated to at least a part thereof, specifically, a polybutadiene resin, a hydrogenated polybutadiene resin, a styrene / butadiene / styrene. Examples thereof include a block copolymer (SBS copolymer), a hydrogenated product thereof (SEBS copolymer), and the like. Among these, a modified product of a hydrogenated product of a styrene / butadiene / styrene block copolymer can be suitably used.

  As a compound for introducing a polar group used for obtaining a modified product of a polymer, a carboxylic acid or a derivative thereof is preferable. For example, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid and fumaric acid; halides, amides, imides, anhydrides and esters of unsaturated carboxylic acids such as maleyl chloride, maleimide, maleic anhydride and citraconic anhydride And the like; and the like. Among these, a modified product with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride is excellent in adhesion, and thus can be suitably used. Among the unsaturated carboxylic acids or anhydrides thereof, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are more preferable, and maleic acid and maleic anhydride are particularly preferable. These unsaturated carboxylic acids and the like can be modified by mixing two or more kinds.

  The method for forming the primer layer is not particularly limited, and examples thereof include a method in which a primer layer forming coating solution is applied on a base film by a known coating method. The thickness of the primer layer is not particularly limited, but is usually 0.01 to 5 μm, preferably 0.1 to 2 μm.

  Moreover, various compounding agents can be added to the resin materials constituting the base film, hard coat layer and primer layer as desired. The compounding agent is not particularly limited as long as it is usually used in thermoplastic resin materials. For example, antioxidants such as phenolic antioxidants, phosphoric acid antioxidants, sulfur antioxidants; UV absorbers such as triazole UV absorbers, benzoate UV absorbers, benzophenone UV absorbers, acrylate UV absorbers, metal complex UV absorbers; light stabilizers such as hindered amine light stabilizers; dyes and pigments Colorants such as: Aliphatic alcohol esters, polyhydric alcohol esters, fatty acid amides, inorganic particles, etc. Lubricants: triester plasticizers, phthalic acid ester plasticizers, fatty acid-basic acid ester plasticizers, oxyacid esters Plasticizers such as plasticizers; antistatic agents such as fatty acid esters of polyhydric alcohols; and the like.

(Low refractive index layer)
The low refractive index layer of the polarizing plate protective film of the present invention contains a specific metal oxide composite and inorganic fine particles, and has a refractive index of 1.25 to 1.37.

The metal oxide complex is formed from one or more compounds selected from the group consisting of the following (a) to (c), and includes — (OM) _m —O— in the molecule. (In the formula, M represents the same meaning as described above, and m represents a natural number.) It has a bond.

(A) A compound represented by formula (1): MX _n .
(B) At least one partial hydrolysis product of the compound represented by the formula (1).
(C) At least one complete hydrolysis product of the compound represented by the formula (1).

In the compound represented by the formula (1) of the above (a), in the formula (1), M represents a metal atom or a metalloid atom.
Examples of the metal atom or metalloid atom include alkali metals such as lithium, sodium and potassium; alkaline earth metals such as magnesium, calcium, barium and strontium; periodic table 3B of boron, aluminum, gallium, indium and thallium Element; Group 4B element of periodic table such as silicon, germanium, tin, lead; Group 5B element of periodic table such as phosphorus, arsenic, antimony; scandium, titanium, vanadium, iron, nickel, copper, zinc, yttrium, Transition metal elements such as zirconium, niobium, tantalum, and tungsten; lanthanoids such as lanthanum, cerium, and neodymium; and the like. Among these, a periodic table group 3B element, a periodic table group 4B element, and a transition metal element are preferable, aluminum, silicon, titanium, and zirconium are more preferable, and silicon (Si) is further preferable.

X is a halogen atom such as a chlorine atom or a bromine atom; a monovalent hydrocarbon group which may have a substituent; an oxygen atom; an organic acid radical such as an acetate radical or a nitrate radical; a β-diketonate such as acetylacetonate A group; an inorganic acid group such as a nitrate group or a sulfate group; an alkoxyl group such as a methoxy group, an ethoxy group, an n-propoxy group or an n-butoxy group; or a hydroxyl group.
N represents the valence of M (metal atom or metalloid atom). When n is 2 or more, X may be the same or different.

Among these, as the compound represented by the formula (1), the formula (2): R _a SiY _4-a [wherein R represents a monovalent hydrocarbon group which may have a substituent] And a represents an integer of 0 to 2, and when a is 2, R may be the same or different. Y represents a hydrolyzable group, and Y may be the same or different. A silicon compound represented by the formula

  Examples of the monovalent hydrocarbon group which may have a substituent include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group; a cyclopentyl group, A cycloalkyl group such as a cyclohexyl group; an aryl group optionally having a substituent such as a phenyl group, a 4-methylphenyl group, a 1-naphthyl group, and a 2-naphthyl group; an alkenyl group such as a vinyl group and an allyl group; Aralkyl groups such as benzyl group, phenethyl group and 3-phenylpropyl group; Haloalkyl groups such as chloromethyl group, γ-chloropropyl group and 3,3,3-trifluoropropyl group; Alkenyl such as γ-methacryloxypropyl group Carbonyloxyalkyl group; an epoxy group having an epoxy group such as γ-glycidoxypropyl group or 3,4-epoxycyclohexylethyl group It can be exemplified a perfluoroalkyl group such as trifluoromethyl group; an alkyl group having an amino group such as 3-aminopropyl group; an alkyl group having a mercapto group such as γ- mercaptopropyl group; kill group. Among these, an alkyl group having 1 to 4 carbon atoms, a phenyl group, and a perfluoroalkyl group are preferable from the viewpoint of ease of synthesis and availability, and a perfluoroalkyl group is preferable from the viewpoint of excellent antifouling properties.

Y represents a hydrolyzable group. Here, the hydrolyzable group refers to a group that is hydrolyzed in the presence of an acid or a base catalyst as desired to form a — (O—Si) _m —O— bond.

  Specific examples of the hydrolyzable group include alkoxyl groups such as methoxy group, ethoxy group and propoxy group; acyloxy groups such as acetoxy group and propionyloxy group; oxime group (—O—N═C—R ′ (R ″)) ), Enoxy group (—O—C (R ′) ═C (R ″) R ′ ″), amino group, aminoxy group (—O—N (R ′) R ″), amide group (—N (R ') -C (= O) -R ") and the like. In these groups, R ′, R ″ and R ′ ″ each independently represents a hydrogen atom or a monovalent hydrocarbon group. Among these, Y is preferably an alkoxyl group from the standpoint of availability. .

  The silicon compound represented by the formula (2) is preferably a silicon compound in which a is an integer of 0 to 2 in the formula (2). Specific examples thereof include alkoxysilanes, acetoxysilanes, oxime silanes, enoxysilanes, aminosilanes, aminoxysilanes, amidosilanes and the like. Among these, alkoxysilanes are more preferable because of their availability.

  In the formula (2), examples of the tetraalkoxysilane in which a is 0 include tetramethoxysilane and tetraethoxysilane. Examples of the organotrialkoxysilane in which a is 1 include methyltrimethoxysilane and methyltriethoxy. Examples include silane, methyltriisopropoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, and the like. Examples of the diorganodialkoxysilane in which a is 2 include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenyldimethoxysilane.

  The molecular weight of the compound represented by the formula (1) is not particularly limited, but is preferably 40 to 300, and more preferably 100 to 200.

  At least one partial hydrolysis product (hereinafter referred to as “compound (3)”) of the compound represented by formula (1) of (b), and represented by formula (1) of (c). At least one complete hydrolysis product of the compound (hereinafter referred to as “compound (4)”) is obtained by fully or partially hydrolyzing one or more of the compounds represented by the formula (1). Can be obtained by condensation.

Compound (3) and compound (4) are, for example, a metal tetraalkoxide represented by M (Or) ₄ (M represents the same meaning as described above, and r represents a monovalent hydrocarbon group). The ratio [H ₂ O] / [Or] can be obtained by hydrolysis in the presence of water in an amount of 1 or more, for example, 1 to 5, preferably 1 to 3.
Hydrolysis can be performed by stirring the whole volume at a temperature of 5 to 100 ° C. for 2 to 100 hours.

  When hydrolyzing the compound represented by the formula (1), a catalyst may be used as necessary. The catalyst to be used is not particularly limited, but the obtained partial hydrolyzate and / or hydrolyzate is likely to have a two-dimensional cross-linked structure, and the condensed compound is easily made porous. From the viewpoint of shortening the time required, an acid catalyst is preferred.

  The acid catalyst to be used is not particularly limited. For example, acetic acid, chloroacetic acid, citric acid, benzoic acid, dimethylmalonic acid, formic acid, propionic acid, glutaric acid, glycolic acid, maleic acid, malonic acid, toluenesulfonic acid, Organic acids such as acids; inorganic acids such as hydrochloric acid, nitric acid, and halogenated silane; acidic sol-like fillers such as acidic colloidal silica and oxidized titania sol; These acid catalysts can be used alone or in combination of two or more.

  Instead of the acid catalyst, a base catalyst such as an aqueous solution of an alkali metal or alkaline earth metal hydroxide such as sodium hydroxide or calcium hydroxide, an aqueous ammonia or an aqueous solution of amines may be used.

  The molecular weights of the compound (3) and the compound (4) are not particularly limited, but usually the weight average molecular weight is in the range of 200 to 5,000.

(Inorganic fine particles)
The inorganic fine particles used in the present invention are not particularly limited as long as they are inorganic compound fine particles. However, inorganic hollow fine particles in which cavities are formed inside the outer shell are preferable, and use of silica-based hollow fine particles is particularly preferable.

As the inorganic compound, an inorganic oxide is common. As the inorganic _{oxide, SiO 2, Al 2 O 3} , B 2 O 3, TiO 2, ZrO 2, SnO 2, Ce 2 O 3, P 2 O 5, Sb 2 O 3, MoO 3, ZnO 2, WO One or two or more of ₃ or the like can be mentioned. Examples of the two or more inorganic oxides include TiO ₂ —Al ₂ O ₃ , TiO ₂ —ZrO ₂ , In ₂ O ₃ —SnO ₂ , and Sb ₂ O ₃ —SnO ₂ . These can be used alone or in combination of two or more.

  As the inorganic hollow fine particles, (A) an inorganic oxide single layer, (B) a single layer of a composite oxide composed of different kinds of inorganic oxides, and (C) a double layer of (A) and (B) above What is included can be used.

The outer shell of the hollow fine particles may be porous having pores, or may be one in which the pores are closed and the cavity is sealed against the outside of the outer shell.
The outer shell is preferably a plurality of inorganic oxide coating layers comprising an inner first inorganic oxide coating layer and an outer second inorganic oxide coating layer. By providing the second inorganic oxide coating layer on the outer side, the fine pores of the outer shell are closed to make the outer shell dense, and furthermore, the inorganic hollow fine particles in which the inner cavity is sealed can be obtained.
In particular, when a fluorine-containing organosilicon compound is used for forming the second inorganic oxide coating layer, the coating layer containing fluorine atoms is formed, so that the resulting particles have a lower refractive index and are reduced to an organic solvent. The dispersibility is good, and further, it is effective for imparting antifouling property to the low refractive index layer, which is preferable.

  Specific examples of such fluorine-containing organosilicon compounds include 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, heptadecafluorodecylmethyldimethoxysilane, hepta. Examples include decafluorodecyltrichlorosilane, heptadecafluorodecyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, and 3,3,3-trifluoropropyltriethoxysilane.

  The thickness of the outer shell is preferably in the range of 1 to 50 nm, particularly 5 to 20 nm. If the thickness of the outer shell is less than 1 nm, the inorganic hollow fine particles may not maintain a predetermined particle shape. On the other hand, when the thickness of the outer shell exceeds 50 nm, the cavities in the inorganic hollow fine particles are small, and as a result, the ratio of the cavities may be reduced and the refractive index may not be sufficiently lowered. Furthermore, the thickness of the outer shell is preferably in the range of 1/50 to 1/5 of the average particle diameter of the inorganic hollow fine particles.

  When the first inorganic oxide coating layer and the second inorganic oxide coating layer are provided as outer shells as described above, the total thickness of these layers may be in the range of 1 to 50 nm. For the densified outer shell, the thickness of the second inorganic oxide coating layer is preferably in the range of 20 to 40 nm.

  The cavity may contain the solvent used when preparing the inorganic hollow fine particles and / or a gas that enters during drying, and a precursor material for forming the cavity described later remains in the cavity. Also good.

  The precursor material is a porous material that remains after removing some of the constituent components of the core particles from the core particles surrounded by the outer shell. As the core particles, porous composite oxide particles made of different types of inorganic oxides are used. The precursor material may remain slightly attached to the outer shell or may occupy most of the interior of the cavity.

  The solvent or gas may be present in the pores of the porous material. When the removal amount of the constituent components of the core particles at this time increases, the volume of the cavity increases, and inorganic hollow fine particles having a low refractive index are obtained. The transparent coating obtained by blending these inorganic hollow fine particles reflects with a low refractive index. Excellent prevention performance.

  The average particle diameter of the inorganic hollow fine particles is not particularly limited, but is preferably in the range of 5 to 2000 nm, and more preferably 20 to 100 nm. If it is smaller than 5 nm, the effect of lowering the refractive index due to hollowness is small. Conversely, if it is larger than 2000 nm, the transparency is extremely deteriorated, and the contribution due to diffuse reflection increases. Here, the average particle diameter is a number average particle diameter by observation with a transmission electron microscope.

  The method for producing inorganic hollow fine particles as described above is described in detail in, for example, Japanese Patent Application Laid-Open No. 2001-233611, and the inorganic hollow fine particles that can be used in the present invention are produced based on the method described therein. In addition, commercially available inorganic hollow fine particles can also be used.

  The blending amount of the inorganic fine particles is not particularly limited, but is preferably 10 to 30% by weight with respect to the entire low refractive index layer. When the blending amount of the inorganic fine particles is within this range, a polarizing plate protective film having both low refractive index properties and scratch resistance can be obtained.

The inorganic fine particles can also be used in the form of a dispersion. The type of the organic solvent used in the dispersion is not particularly limited. For example, lower aliphatic alcohols such as methanol, ethanol, isopropanol (IPA), n-butanol, isobutanol; ethylene glycol, ethylene glycol mono Ethylene glycol derivatives such as butyl ether and ethylene glycol monoethyl ether; diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; diacetone alcohol; aromatic hydrocarbons such as toluene and xylene; aliphatic carbons such as n-hexane and n-heptane Hydrogen; Esters such as ethyl acetate and butyl acetate; Ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone;
These organic solvents can be used alone or in combination of two or more.

  The low refractive index layer is a composition containing a metal oxide composite selected from the group consisting of the above (a) to (c) and at least one kind of inorganic fine particles (hereinafter referred to as “coating composition”). Can be formed on the base film and, if necessary, dried and heat-treated.

  The coating composition may be applied to the surface of the base film to form a coating film, and it may be preferable that at least partial hydrolysis of the matrix-forming material occurs. It is preferable to contain a mixture with an organic solvent.

  Examples of the organic solvent to be used include lower aliphatic alcohols such as methanol, ethanol, isopropanol (IPA), n-butanol, and isobutanol; ethylene glycol derivatives such as ethylene glycol, ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether acetate. And hydrophilic organic solvents such as diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; diacetone alcohol; and combinations of two or more thereof.

  In combination with the hydrophilic organic solvent, aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as n-hexane and n-heptane; esters such as ethyl acetate and butyl acetate; methyl ethyl ketone and methyl Ketones such as isobutyl ketone; oximes such as methyl ethyl ketoxime; and combinations of two or more of these; and the like can be used.

  When the coating composition contains the compounds (a) and (b), it preferably contains a curing catalyst. As a result, when the coating composition is applied to the surface of the substrate film to form a coating film and dried, the condensation reaction is promoted to increase the crosslinking density in the coating film, thereby improving the water resistance and alkali resistance of the coating film. The effect which can be improved can be acquired.

  Examples of the curing catalyst to be used include metal chelate compounds such as Ti chelate compounds and Zr chelate compounds; organic acids and the like.

  The coating composition may further contain a known silane coupling agent. When the low refractive index layer is formed on the base film using the coating composition by including the silane coupling agent, the adhesion between the base film and the low refractive index layer may be improved. is there.

  A method for coating the coating composition on the base film is not particularly limited, and a known coating method can be employed. Examples of the coating method include a wire bar coating method, a dip method, a spray method, a spin coating method, and a roll coating method.

  The temperature at which the coating composition is applied is usually 10 to 40 ° C., preferably 20 to 30 ° C., and the relative humidity is usually 10 to 80%, preferably 40 to 70%.

When a coating layer is obtained by coating the coating composition, and then the coating layer is dried, it is preferably dried under conditions of a drying temperature of 20 to 130 ° C. and a relative humidity of 0 to 80%. Drying is performed at a drying temperature of 20 to 80 ° C. and a relative humidity of 0 to 80% until the amount of solvent remaining in the coating layer reaches 5% by weight, and then the amount of solvent remaining in the coating layer is 5% by weight. If it becomes less than it, it is more preferable to dry on conditions with a drying temperature of 80-130 degreeC, and a relative humidity of 0-20%.
The thickness of the obtained low refractive index layer is usually 10 to 1000 nm, preferably 50 to 500 nm.

The refractive index of the low refractive index layer is 1.25 to 1.37, preferably 1.25 to 1.36, particularly preferably 1.25 to 1.35.
When the refractive index of the low refractive index layer is less than 1.25, the strength of the low refractive index layer is weak, and the desired scratch resistance required as a polarizing plate protective film may not be obtained. On the other hand, if it exceeds 1.37, the desired antireflection effect may not be obtained.
The refractive index can be obtained by measuring using, for example, a known spectroscopic ellipsometer.

  Further, the reflectance of the low refractive index layer is usually 0.5% or less, preferably 0.3%. The reflectance can be obtained as a reflectance at a wavelength of 550 nm by measuring a reflection spectrum at a predetermined incident angle using, for example, a known spectrophotometer.

  The polarizing plate protective film of the present invention can further form an antifouling layer on the low refractive index layer in order to protect the low refractive index layer and enhance the antifouling performance.

  The material for forming the antifouling layer is not particularly limited as long as the function of the low refractive index layer is not inhibited and the required performance as the antifouling layer is satisfied. Usually, a compound having a hydrophobic group can be preferably used. As specific examples, a perfluoroalkylsilane compound, a perfluoropolyethersilane compound, or a fluorine-containing silicone compound can be used. As the method for forming the antifouling layer, for example, a physical vapor deposition method such as vapor deposition or sputtering; a chemical vapor deposition method such as CVD; a wet coating method; The thickness of the antifouling layer is not particularly limited, but is usually preferably 20 nm or less, and more preferably 1 to 10 nm.

  The polarizing plate protective film of the present invention is formed into a film having an average thickness of 50 μm and a size of 100 mm × 100 mm, and has a warpage rate of 1% or less when left in an atmosphere of 60 ° C. and humidity of 95% for 500 hours. preferable. When such a polarizing plate protective film is used, even if it is left for a long time under high humidity and high temperature, the warping rate is as small as 1% or less, so the base film and the low refractive index Excellent adhesion to layers and processability when bonded to other films.

  Specifically, the warpage rate can be obtained as follows. First, the polarizing plate protective film 1 of the present invention is cut into an average thickness of 50 μm and a size of 100 mm × 100 mm. Next, this is left in an atmosphere of 60 ° C. and 95% humidity for 500 hours. Next, as shown in FIG. 1, the polarizing plate protective film 1 after the test is allowed to stand on the horizontal surface plate 2, and the distance h (nm) from the surface plate surface to the lower side of the portion farthest from the surface plate surface is vernier caliper. And the ratio of the distance to the length (100 mm) of the polarizing plate protective film is obtained as the warpage rate (%). That is, the warpage rate (%) can be obtained by the formula: warpage rate (%) = h / 100 × 100. In addition, when the polarizing plate protective film 1 is left in an atmosphere of 60 ° C. and a humidity of 95% for 500 hours, it may be deformed into a convex shape or a concave shape. Thus, the polarizing plate protective film 1 after the test is placed on the horizontal surface plate 2 so that the lower side is convex, and the distance (h) is measured.

Further, the polarizing plate protective film of the present invention is excellent in scratch resistance, and is particularly useful as a polarizing plate protective film for liquid crystal display devices that require scratch resistance.
The polarizing plate protective film of the present invention is a film surface in visual observation even after a test (steel wool test) in which the surface of the polarizing plate protective film is rubbed 10 times with a load of 0.025 MPa applied to steel wool. There are no scratches.

  In the polarizing plate protective film of the present invention, the change in the total light transmittance before and after the steel wool test is extremely small. Here, change rate of total light transmittance (%) = (change amount of total light transmittance before and after test) / (total light transmittance before test) × 100. The change rate of the total light transmittance is preferably 1% or less.

  In the polarizing plate protective film of the present invention, the change in haze value before and after the steel wool test is extremely small. Here, haze change rate (%) = (haze change amount before and after test) / (haze before test) × 100, the haze change rate of the polarizing plate protective film of the present invention is 15% or less. Preferably there is.

  The layer structural example of the polarizing plate protective film of this invention is shown in FIG. A polarizing plate protective film 20 shown in FIG. 2 has a hard coat layer 12 formed on a base film 10, and a low refractive index layer 14 containing hollow fine particles 14 a is laminated on the hard coat layer 12. It has a structure. The polarizing plate protective film of this invention is not limited to what is shown in FIG. 2, What is necessary is just to have a low refractive index layer at least on a base film. For example, the thing of the structure by which the low-refractive-index layer was directly formed on the base film may be sufficient.

  The polarizing plate protective film of the present invention is, for example, a mobile phone, a digital information terminal, a pager (registered trademark), navigation, a liquid crystal display for vehicle use, a liquid crystal monitor, a light control panel, a display for OA equipment, a display for AV equipment, etc. Various liquid crystal display elements; useful as protective films for polarizing plates such as touch panels.

3) Polarizing plate with antireflection function The polarizing plate with antireflection function of the present invention is characterized in that the polarizing plate protective film of the present invention is used on the viewing side of the protective film of the polarizing plate.

  The polarizing plate is not particularly limited as long as it has a function as a polarizing plate. For example, a polyvinyl alcohol (PVA) -based or polyene-based polarizing plate can be used.

  The manufacturing method of a polarizing plate is not specifically limited. As a method of manufacturing a PVA-based polarizing plate, a method of stretching uniaxially after iodine ions are adsorbed on a PVA-based film, a method of adsorbing iodine ions after stretching a uniaxially stretched PVA-based film, A method of simultaneously performing iodine ion adsorption and uniaxial stretching, a method of stretching a uniaxial film after dyeing a PVA film with a dichroic dye, a method of stretching a uniaxial film and then adsorbing with a dichroic dye, a PVA system The method of performing simultaneously dyeing | staining with a dichroic dye and uniaxial stretching to a film is mentioned. In addition, as a method for producing a polyene-based polarizing plate, a method of heating and dehydrating in the presence of a dehydration catalyst after stretching a PVA-based film uniaxially, and in the presence of a dehydrochlorination catalyst after stretching a polyvinyl chloride-based film uniaxially. And publicly known methods such as heating and dehydrating.

  The polarizing plate with an antireflection function of the present invention can be produced by laminating a polarizing plate on one surface of the base film of the polarizing plate protective film of the present invention where the low refractive index layer is not provided.

  Lamination | stacking with a polarizing plate protective film and a polarizing plate can be bonded together using appropriate adhesion means, such as an adhesive agent and an adhesive. Examples of the adhesive or pressure-sensitive adhesive include acrylic, silicone, polyester, polyurethane, polyether, rubber, and the like. Among these, from the viewpoint of heat resistance and transparency, it is preferable to use an acrylic material.

  In the polarizing plate with an antireflection function of the present invention, a protective film may be laminated via an adhesive or an adhesive layer on the surface of the polarizing plate on which the polarizing plate protective film of the present invention is not laminated. Good. As a protective film, what consists of material with low optical anisotropy is preferable. The material having low optical anisotropy is not particularly limited, and examples thereof include cellulose esters such as triacetyl cellulose and alicyclic structure-containing polymer resins. However, transparency, low birefringence, dimensional stability, etc. From the standpoint of superiority, an alicyclic structure-containing polymer resin is preferred. Examples of the alicyclic structure-containing polymer resin include those described in the explanation part of the base film. Examples of the adhesive or pressure-sensitive adhesive include those similar to the adhesive or pressure-sensitive adhesive used for laminating the polarizing plate protective film and the polarizing plate.

  FIG. 3 shows a sectional view of the layer structure of the polarizing plate with antireflection function of the present invention. The polarizing plate 30 with an antireflection function shown in FIG. 3 has a polarizing plate 18 on the surface side of the polarizing plate protective film 20 of the present invention on which the low refractive index layer 14 is not provided, with an adhesive or pressure-sensitive adhesive layer 16 interposed therebetween. Is further laminated, and the protective film 10a is laminated on the surface side that is the viewing side of the polarizing plate 18 with an adhesive or pressure-sensitive adhesive layer 16 interposed therebetween.

  Since the polarizing plate with an antireflection function of the present invention uses the polarizing plate protective film of the present invention, even when it is placed in a high temperature / high humidity environment for a long time, it is warped, deformed or distorted as a whole. Thus, the polarizing plate has a structure in which, for example, it is difficult to occur. Moreover, it is excellent in interlayer adhesion, and even when it is left for a long time under high temperature and high humidity, delamination does not occur.

4) Optical product The optical product of the present invention includes the polarizing plate with an antireflection function of the present invention. Preferable specific examples of the optical product of the present invention include a liquid crystal display device and a touch panel.

  As an example of an optical product including the polarizing plate with antireflection function of the present invention, FIG. 4 shows a layer configuration example of a liquid crystal display device including the polarizing plate with antireflection function of the present invention. The liquid crystal display device shown in FIG. 4 includes a polarizing plate 40, a retardation plate 50, a liquid crystal cell 60, and the polarizing plate 30 with an antireflection function of the present invention in order from the bottom. The polarizing plate 30 with an antireflection function is formed on the liquid crystal cell 60 by being bonded to the polarizing plate surface via an adhesive or pressure-sensitive adhesive layer (not shown). In the liquid crystal cell 60, for example, as shown in FIG. 5, two electrode substrates 80 each having a transparent electrode 70 are arranged at a predetermined interval with the transparent electrodes 70 facing each other, and a liquid crystal 90 is disposed in the gap. It is produced by enclosing. In FIG. 5, 100 is a seal.

  The liquid crystal mode of the liquid crystal 90 is not particularly limited. As the liquid crystal mode, for example, a TN (twisted nematic) type, an STN (super twisted nematic) type, an IPS (in-plane switching) type, a VA (vertical alignment) type, an MVA (multi-domain angry type) Examples include a Hybrid Aligned Nematic type and an OCB (Optical Compensated Bend) type.

  In addition, the liquid crystal display device shown in FIG. 4 has a normally white mode that is bright when the applied voltage is low, a dark display when the applied voltage is high, a dark display when the applied voltage is low, and a normally black mode that is bright when the applied voltage is high. Can be used.

  The optical product of the present invention includes the polarizing plate with an antireflection function of the present invention that is excellent in durability without causing deformation or stress in use under high temperature and high humidity. Therefore, even when used for a long time under high temperature and high humidity, there is no color loss at the end of the display panel, hue variation within the display panel surface, or the like.

  Next, the present invention will be described in more detail with reference to examples. The present invention is not limited to the following examples.

(1) Refractive index Using a high-speed spectroscopic ellipsometer (manufactured by JA Woollam, M-2000U), measurement is performed at a measurement wavelength of 245 to 1000 nm, incident angles of 55 degrees, 60 degrees, and 65 degrees. Based on calculations.

(2) Reflectance Using a spectrophotometer (manufactured by JASCO Corporation, UV-visible near-infrared spectrophotometer V-570), the reflection spectrum was measured at an incident angle of 5 degrees, and the reflectance at a wavelength of 550 nm was determined. .

(3) Scratch resistance Steel wool test An operation of rubbing the surface of the polarizing plate protective film 10 times in a state where a load of 0.025 MPa was applied to steel wool # 0000 (hereinafter referred to as "steel test") was performed. The following (i) and (ii) were evaluated.
(I) Appearance of film after steel test The degree of damage on the surface of the film after the steel test was visually observed and evaluated according to the following evaluation criteria.
(Double-circle): A crack is not recognized.
○: Slightly weak scratches can be seen when looking carefully.
X: Scratches are observed.

(Ii) Change in total light transmittance and haze before and after steel test (according to ASTM D1003)
Using “Durbidity Meter NDH-300A” manufactured by Nippon Denshoku Industries Co., Ltd., it was performed according to ASTM D1003. This was carried out for 5 samples.

(4) Warpage rate (deformation) of polarizing plate protective film
As shown in FIG. 1, after leaving a test piece of 100 mm × 100 mm at 60 ° C. and 95 RH% for 500 hours, place the test piece on a horizontal surface plate in a direction in which it protrudes downward. The distance h (mm) to the lower side of the far part was measured with a caliper, and the ratio of the distance to the length of the sample was defined as the warpage rate (%). That is, the warpage rate (%) = h / 100 × 100. At that time, in the case of a convex warp on the film forming side, the warping rate was expressed as a positive value, and in the case of a concave warp on the film forming side, the warping rate was expressed as a negative value.

  For 100 parts by weight of norbornene-based polymer (hydrogenated ring-opening copolymer of norbornene-based monomer, manufactured by Nippon Zeon Co., Ltd., trade name: ZEONOR 1430, glass transition temperature (Tg) = 145 ° C.), 0.2 parts by weight of a phenolic antioxidant pentaerythrityl-tetrakis [3- (3,5-di-tertiarybutyl-4-hydroxyphenyl) propionate] was mixed and kneaded in a twin-screw kneader, A strand (rod-shaped molten resin) was passed through a strand cutter to obtain a pellet (granular) shaped molding material.

The pellets obtained above were dried at 110 ° C. for 4 hours using a hot air dryer in which air was circulated. The pellets were then used in a T-die film melt extrusion machine having a resin melt kneader equipped with a 65 mmφ screw equipped with a leaf disk-shaped polymer filter (filtration accuracy 30 μm), and the surface roughness Ra = The sheet-shaped norbornene-based polymer was extruded using a 350 mm wide T-shaped die having a chromium plating of 0.15 μm at a molten resin temperature of 260 ° C. and a die temperature of 260 ° C. , Temperature: 135 ° C., circumferential speed R ₁ : 10.05 m / min), then second cooling drum (diameter 250 mm, temperature: 125 ° C., circumferential speed R ₂ : 10.05 m / min), then third cooling drum (diameter 250 mm, temperature: 100 ° C., circumferential speed _R 3: _9.98m / min) were sequentially close contact with transported, length 300 meters, film The substrate film 1A of 40μm was extruded. The obtained long base film 1A was wound up in a roll shape. Moreover, content of the volatile component of this base film 1A was 0.01 weight% or less, and the saturated water absorption was 0.01 weight% or less.

(Preparation of hard coat agent 1)
Hexafunctional urethane acrylate oligomer (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name “NK Oligo U-6HA”) 30 parts, butyl acrylate 40 parts, isobornyl methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name “NK ester” IB ") 30 parts and 2,2-dimethoxy-1,2-diphenylethane-1-one 10 parts were mixed with a homogenizer to prepare a hard coat agent 1 comprising an ultraviolet curable resin composition.

(Preparation of hard coating agent 2)
Antimony pentoxide modified alcohol sol (solid content 30% by weight, manufactured by Catalytic Chemical Co., Ltd.) 100 parts by weight, UV curable urethane acrylate (manufactured by Nippon Synthetic Chemical Co., Ltd., trade name “purple light UV7000B”), 10 parts by weight, photopolymerization An initiator (manufactured by Ciba Specialty Chemicals, trade name “Irgacure 184” 0.4 parts by weight was mixed to prepare an ultraviolet curable hard coat agent 2.

(Manufacture example 1) Manufacture of hard-coat layer laminated | multilayer film 2A On both surfaces of the base film 1A obtained above, using a high frequency transmitter (Corena generator HV05-2, the product of Tamec), output voltage 100%, output Corona discharge treatment was performed for 3 seconds under the conditions of 250 W, a wire electrode having a diameter of 1.2 mm, an electrode length of 240 mm, and a work electrode distance of 1.5 mm, and the surface was modified so that the surface tension was 0.072 N / m. The hard coat agent 1 was continuously applied thereon using a die coater so that the thickness of the hard coat layer after curing was 5 μm. Subsequently, after drying at 80 degreeC for 5 minute (s), ultraviolet irradiation (integrated light quantity 300mJ / cm < ² >) was performed, the hard-coat agent was hardened, and hard-coat layer laminated film 2A was obtained.

(Production Example 2) Production of hard coat layer laminated film 2B Triacetyl cellulose (TAC) film having a thickness of 40 μm (base film 1B, manufactured by Konica Minolta, KC4UX2M, Tg = 120 ° C., saturated water absorption = 4 Hard coat layer laminated film 2B was obtained in the same manner as in Production Example 1, except that 0.5 wt% and volatile component content = 6.0 wt% were used.

(Production Example 3) Production of hard coat layer laminated film 2C In the same manner as in Production Example 1, except that a polyethylene terephthalate film (base film 1C, manufactured by Toray Industries, Inc., Lumirror T60) having a thickness of 40 μm was used. -Coated layer laminated film 2C was obtained.

Production Example 4 Preparation of Coating Composition 1 A mass ratio of 21: 36: 2: 2 of an oligomer of tetotamethoxysilane (manufactured by Colcoat Co., Ltd., methyl silicate 51), methanol, water, and 0.01N hydrochloric acid aqueous solution. The mixture was stirred for 2 hours in a high-humidity bath at 25 ° C. to obtain a silicone resin having a weight average molecular weight adjusted to 850. Next, hollow silica isopropanol dispersion sol (manufactured by Catalyst Kasei Co., Ltd., solid content 20% by weight, average primary particle diameter of about 35 nm, outer shell thickness of about 8 nm) is added to the silicone resin as hollow silica fine particles, A silicone resin (condensed compound equivalent) is blended so that the weight ratio is 7: 3 based on the solid content, and then diluted with methanol so that the total solid content is 1% by weight, to obtain a coating composition 1 It was.

(Production Example 5) Preparation of Coating Composition 2 Hollow silica fine particles / silicone resin (condensation compound equivalent) were blended so that the weight ratio was 8: 2 on a solid content basis, and there was a cavity inside the outer shell. Silica methanol (manufactured by Nissan Chemical Industries, Ltd., PMA-ST, average particle diameter of 10 to 20 nm) is used as the silica fine particles that are not formed, and this is used as the solid content in terms of SiO _{2 with} respect to the total solid content of the coating composition The coating composition 2 was prepared in the same manner as the coating composition 1 except that 5% was added.

(Production Example 6) Preparation of Silicon Alkoxide Solution 1 Liquid A was prepared by mixing tetramethoxysilane oligomer (manufactured by Colcoat Co., Ltd., methyl silicate 51) and methanol at a mass ratio of 47:71. In addition, liquid B was prepared by mixing water, aqueous ammonia (28 wt%), and methanol in a weight ratio of 60: 1.2: 97.2. And A liquid and B liquid were mixed by ratio of 16:17, and the silicon alkoxide solution 1 was prepared.

(Production Example 7) Preparation of Silicon Alkoxide Solution 2 Silicone alkoxide solution 2 was prepared in the same manner as in Production Example 6 except that when liquid A was prepared, an oligomer of tetramethoxysilane and methanol were mixed at a weight ratio of 47:79. did.

Example 1
The coating composition 1 obtained in Production Example 4 was allowed to stand for 1 hour after preparation, and then the composition 1 was applied onto the hard coat layer laminated film 2A with a wire bar coater to give a coating having a thickness of about 100 nm. After forming a film and allowing it to stand for 1 hour to dry, the film was heat-treated in air at 120 ° C. for 10 minutes to obtain a polarizing plate protective film 3A on which a cured film was formed.

(Example 2)
A polarizing plate protective film 3B on which a cured film was formed was obtained in the same manner as in Example 1 except that the coating composition 2 obtained in Production Example 5 was used.

(Example 3)
A polarizing plate protective film 3C on which a cured film was formed was obtained in the same manner as in Example 2 except that the hard coat laminated film 2B of Production Example 2 was used.

(Example 4)
A polarizing plate protective film 3D on which a cured film was formed was obtained in the same manner as in Example 2 except that the hard coat laminated film 2C of Production Example 3 was used.
(Example 5)
A polarizing plate protective film 3E on which a cured film was formed was obtained in the same manner as in Example 1 except that the hard coating agent 2 was used instead of the hard coating agent 1.

(Comparative Example 1)
The silicon alkoxide solution 1 obtained in Production Example 6 was dropped on the hard coat layer laminated film 2B of Production Example 2 after 1 minute from the start of mixing and spin-coated. The rotation chamber of the spin coater was in a methanol atmosphere, and rotation was performed at 700 rpm for 10 seconds. After coating, the film was left for 1 minute and 15 seconds to obtain a thin film in which silicon alkoxide was gelled.
This gel-like thin film was immersed in a curing solution having a composition in which water, 28% aqueous ammonia, and methanol were mixed at a mass ratio of 162: 4: 640 for 5 minutes, and then cured at room temperature all day and night. Furthermore, this thin film was immersed in a 10% isopropanol solution of hexamethyldisilazane to perform a hydrophobic treatment.
Next, this hydrophobized gel compound is washed by immersing it in isopropanol, placed in a high-pressure vessel, filled with liquefied carbon dioxide gas, and supercritically dried at 80 ° C., 16 MPa for 2 hours, A polarizing plate protective film 3F having a silica airgel thin film with a thickness of 100 nm formed on the surface was obtained.

(Comparative Example 2)
A polarizing plate protective film 3G was obtained in the same manner as in Comparative Example 1 except that the silicon alkoxide solution 2 obtained in Production Example 7 was used when forming the low refractive index layer.

  Using the polarizing plate protective films 3A to 3E of Examples 1 to 5 obtained above and the polarizing plate protective films 3F and 3G of Comparative Examples 1 and 2, the refractive index of the low refractive index layer and the hard coat layer, The reflectance, the appearance of the film after the steel test, the total light transmittance and haze before and after the steel wool test, and the warpage rate (%) were measured. The measurement results for the polarizing plate protective films 3A to 3G are summarized in Table 1.

From Table 1, the polarizing plate protective films 3A to 3E of Examples 1 to 5 have a low refractive index of the low refractive index layer and a low reflectance, and are useful as an optical film having an antireflection function. It is suggested.
In the polarizing plate protective films 3A to 3E of Examples 1 to 5, no scratches were observed on the surface by visual observation after the steel wool test, and the changes in the total light transmittance and the haze value before and after the steel wool test were small. And excellent in scratch resistance.
Moreover, the polarizing plate protective films 3A-3E of Examples 1-5 also have a small curvature rate of a film.

On the other hand, the polarizing plate protective film 3F of Comparative Example 1 has a low refractive index and a low reflectance, but has a high haze value after the steel wool test and is inferior in scratch resistance. .
In addition, the polarizing plate protective film 3G of Comparative Example 2 has small changes in the total light transmittance and haze value before and after the steel wool test and excellent scratch resistance, but the refractive index and reflectance of the low refractive index layer are low. Large and inferior in antireflection function.

(Examples 6 to 10, Comparative Examples 3 and 4) Production of liquid crystal display element (1) Production of polarizing plate with antireflection function Polyvinyl alcohol film having a polymerization degree of 2400 and a thickness of 75 μm was mixed with iodine and potassium iodide. After dipping in a dye bath at ℃ and dyeing treatment, in the acid bath at 60 ℃ with boric acid and potassium iodide added, stretch treatment and crosslinking treatment are performed so that the total draw ratio is 5.3 times. It was. After washing with water, it was dried at 40 ° C. to obtain a polarizing plate having a thickness of 28 μm.

  The polarizing plate is bonded to the base film 1A surface side of the polarizing plate protective film 3A obtained in Example 1 via an acrylic adhesive (manufactured by Sumitomo 3M, "DP-8005 clear"), and polarized. A polarizing plate 4A with an antireflection function having the same layer structure as that shown in FIG. 3 is bonded to the other surface side of the plate with a surface-modified base film 1A via an acrylic adhesive. Produced. Moreover, the same operation was performed using polarizing plate protective film 3B-3G, and polarizing plate 4B-4G with an antireflection function was obtained, respectively.

(2) Production of liquid crystal display element A liquid crystal display cell (3 inches, thickness of the plastic substrate 400 μm) using a plastic cell substrate is prepared, and the front side of the liquid crystal display cell and the polarizing plate 4A to 4 with antireflection function obtained above. The 4G polarizing plate side was bonded. Further, another polarizing plate was prepared, and this was used for the rear, and was bonded to the opposite surface of the liquid crystal display cell, thereby producing liquid crystal display elements. This liquid crystal display element is left in an environment of 60 ° C. and 95% RH for 500 hours and then placed on a backlight having an illuminance of 33,000 lux. The hue variation was visually observed. ○ when there is no light leakage near the edge of the panel and a uniform black display is obtained, △ when there is some light leakage near the edge of the panel, and when away from the panel edge (panel surface (Inside), light leakage was observed and hue variation was evaluated as x. The evaluation results are shown in Table 2.

  From Table 2, the display performance of the liquid crystal display elements of Examples 6 to 10 is not deteriorated even when placed in a high temperature and high humidity environment for a long time. On the other hand, the liquid crystal display elements of Comparative Examples 3 and 4 show a decrease in display performance after being placed in a high temperature and high humidity environment for a long time.

The polarizing plate protective film of the present invention has a low refractive index layer that is effective as an antireflection layer, and has sufficient scratch resistance as a protective film for a polarizing plate. Moreover, it is a film with little warp (deformation) of a film which becomes a problem at the time of bonding with a polarizing plate.
Since the polarizing plate with antireflection function of the present invention uses the protective film of the present invention as at least one of the protective films of the polarizing film, it has both an excellent antireflection function and scratch resistance. Further, there is little warpage (deformation) that becomes a problem when the protective film and the polarizing plate are bonded together.
Since the polarizing plate with an antireflection function of the present invention uses the polarizing plate protective film of the present invention, even when it is placed in a high temperature / high humidity environment for a long time, it is warped, deformed or distorted as a whole. Thus, the polarizing plate has a structure in which, for example, it is difficult to occur.

Claims (10)

A polarizing plate protective film having a base film and a low refractive index layer formed on the base film,
The low refractive index layer has the formula (1): MX _n (wherein M represents a metal atom or a metalloid atom, X represents a halogen atom, a monovalent hydrocarbon group which may have a substituent, An oxygen atom, an organic acid group, a β-diketonate group, an inorganic acid group, an alkoxyl group or a hydroxyl group, and n represents a valence of M. When n is 2 or more, X may be the same or different. A group consisting of at least one partial hydrolysis product of the compound represented by the formula (1) and at least one complete hydrolysis product of the compound represented by the formula (1) A metal oxide having a bond of-(OM) _m -O- (wherein M represents the same meaning as described above and m represents a natural number) formed in one or more types selected from Containing a composite material and inorganic fine particles and having a refractive index of 1.25 to 1.37 Polarizing plate protective film characterized in that there.   The polarizing plate protective film according to claim 1, wherein the inorganic fine particles are hollow fine particles of an inorganic compound.   The polarizing plate protective film according to claim 1, wherein the M is Si.   The polarizing plate protective film according to claim 1, wherein a hard coat layer is interposed between the base film and the low refractive index layer.   The polarizing plate protective film according to claim 4, wherein the hard coat layer contains an active energy ray-curable resin or a thermosetting resin.   The polarizing plate protective film according to claim 4, wherein a refractive index of the hard coat layer is 1.53 or more.   The polarizing plate protective film according to claim 4, wherein the hard coat layer further contains conductive fine particles.   The said base film consists of alicyclic structure containing polymer resin, The polarizing plate protective film in any one of Claims 1-7 characterized by the above-mentioned.   A polarizing plate with an antireflection function, wherein the polarizing plate protective film according to claim 1 is used on the viewing side of the protective film of the polarizing plate. An optical product comprising the polarizing plate with an antireflection function according to claim 9.

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